CN114324681A - High-throughput method for detecting content of nitro polycyclic aromatic hydrocarbon - Google Patents
High-throughput method for detecting content of nitro polycyclic aromatic hydrocarbon Download PDFInfo
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Abstract
The invention provides a high-throughput method for detecting the content of nitro polycyclic aromatic hydrocarbon, belongs to the technical field of detection methods, provides a novel rapid-dispersion solid-phase extraction material multi-walled carbon nanotube/polyaniline polymer with strong applicability, and provides a preparation method of the multi-walled carbon nanotube/polyaniline polymer.
Description
Technical Field
The invention belongs to the technical field of detection methods, relates to a high-flux method for detecting the content of nitro polycyclic aromatic hydrocarbon, and particularly relates to a rapid pretreatment and high-flux detection method for nitro polycyclic aromatic hydrocarbon in rice crops and soil media thereof.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are persistent organic pollutants widely existing in food and environmental media, are environmental carcinogenic compounds discovered earlier, mostly have triple toxicity, nitro Polycyclic Aromatic Hydrocarbons (N-PAHs) are nitro substitutes of Polycyclic Aromatic Hydrocarbons, are different from PAHs, and N-PAHs can directly display mutagenic activity without adding any biological enzyme, and have toxicity 2-10 times higher than that of PAHs. Toxicology and epidemiological research shows that the N-PAHs can enter the human body through the ways of respiratory intake or dietary intake and the like to accumulate and induce tumors and canceration of a plurality of parts, damage the central nerve and influence the health of the human body. Meanwhile, N-PAHs in the soil environment can enter crops through atmospheric sedimentation or root absorption and other ways and accumulate in the body, and further can form potential threat to human health through the transmission and amplification of a food chain.
The rice is one of the main grain crops in China and is staple food for daily ingestion of residents. In recent years, human harmful factors such as aromatic hydrocarbons and substituted organic pollutants thereof, which are widely present in environmental media such as soil, have been drawing attention. Developed countries have established strict test procedures and residual limits on food PAHs residual standards, such as the european union published (EU)2020/1255 document that defines the maximum residual limits of PAHs in plant-derived foods. Benzo [ a ] in food of national standard GB 5009.27-2016 for food safety in China, which is imported and exported as agricultural products in great countries]The determination of pyrene and the determination of polycyclic aromatic hydrocarbon in GB 5009.265-2016 food stipulate the detection method of various PAHs such as BaP in cereal and grain crop food, and adopts the traditional carbon material C18And the dispersed solid phase extraction pretreatment of PSA filler, wherein the detection limit and the quantification limit of the liquid chromatography are respectively 0.33-3.3 mu g/kg and 1.0-10 mu g/kg. The environmental standard HJ 784-2016 (high performance liquid chromatography for measuring polycyclic aromatic hydrocarbons in soil and sediments) stipulates the test operation process of 16PAHs preferentially controlled in the United states, silica gel chromatography columns or solid phase extraction columns which take silica gel or silica magnesium as fillers are adopted for purification, and the samples are injected after nitrogen blowing concentration. A new design of Lu' ezui18The technology for simultaneously measuring 16PAHs in paddy and soil by PSA filler has the detection limit of 0.05-2.0 mu g/L (reference: Lv 'an' er, Shi Lei, Cai Xiao Hu, etc.. QuEChERS-high performance liquid chromatography for rapidly measuring 16 polycyclic aromatic hydrocarbons [ J ] in paddy and soil]Physicochemical examination (chemical breakdown), 2016,52(9): 1017-. However, such methods are either complicated in procedure or expensive in cost, and difficult to perform at the basic levelThe detection mechanism is popularized and applied, and mostly focuses on the detection of polycyclic aromatic hydrocarbons, but the research on the nitro polycyclic aromatic hydrocarbons N-PAHs is rarely reported.
Therefore, the development of novel materials for the high-flux, multi-component and simultaneous on-line rapid residue detection of N-PAHs in fast, efficient, green and clean grain crops and environmental media thereof is urgently needed.
Disclosure of Invention
The current dispersive solid-phase extraction is a research on a novel internationally favored sample pretreatment method, a high-efficiency specific adsorption material is prepared by improving a green product synthesis method, and optimal selection of an extraction solvent is compared and screened, so that the aims of reducing environmental pollution and improving the detection efficiency and sensitivity of the method are fulfilled, and the method is a key step for realizing high-throughput, multi-component and simultaneously on-line accurate detection and analysis.
Based on the above, the application aims to develop a novel fast-dispersing solid-phase extraction material with strong applicability, and the material with controllable particle size, high recycling rate and strong adsorption performance is prepared and synthesized to perform double fast extraction analysis of rice and soil, so that a simple, fast and efficient key sample analysis technology is realized, and further a high-throughput detection method for nitro polycyclic aromatic hydrocarbon in rice crops and soil media thereof is realized.
Explanation of chemical name abbreviations:
PSA is ethylene diamine-N-propyl silanized silica gel: 40-60 μm.
C18Octadecylsilane chemically bonded silica: 40-60 μm.
MWCNTs are multiwalled carbon nanotubes: 15-25nm
PANI is polyaniline.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the invention provides a multi-walled carbon nanotube/polyaniline, which can be used for double rapid extraction of rice and soil.
The invention also provides a preparation method of the multi-walled carbon nanotube/polyaniline, which comprises the following steps: putting the multi-walled carbon nano-tube into a three-neck flask, adding an emulsifier, a co-emulsifier, a dopant and an initiator into the three-neck flask, and preparing the multi-walled carbon nano-tube/polyaniline polymer by adopting an emulsion polymerization method.
The emulsifier is dodecyl alcohol polyoxyethylene ether sulfuric acid;
the auxiliary emulsifier is cetearyl alcohol;
the dopant is hydrochloric acid;
the initiator is ammonium persulfate;
the reaction temperature of the emulsion polymerization method is 0-4 ℃, and the reaction time is 5-6 h;
the molar ratio of the emulsifier to the co-emulsifier to the dopant to the initiator is 2.8:4:1: 5.
Further, the preparation method of the multi-walled carbon nanotube/polyaniline comprises the following steps: introducing nitrogen into a round-bottom three-mouth flask to remove oxygen, adding 2.0-5.0g of multi-walled carbon nano tube and 10.0-15.0mL of ethanol, ultrasonically homogenizing for 30 seconds for a short time, adding 50-100mL of deionized water and 0.025-0.10mol of first aniline, adding lauryl alcohol polyoxyethylene ether sulfuric acid and cetostearyl alcohol, quickly stirring at a constant temperature for 10-20min at a high speed, then adding 0.025-0.10mol of second aniline, finally adding 0.05-0.20mol of hydrochloric acid, controlling the reaction temperature in an ice bath state, continuously stirring for 30-50min, dropwise adding 0.05-0.20mol of ammonium persulfate aqueous solution, continuously stirring at a high speed for reacting for 6-10h, and obtaining a product after the reaction is finished; demulsifying the product with acetone, filtering the emulsion with a G3/G4 funnel, centrifuging, repeatedly washing with acetone-water to neutrality, and vacuum drying at 60-80 deg.C to obtain the multi-walled carbon nanotube/polyaniline polymer.
In the preparation method, the molar ratio of the first part of aniline to the lauryl alcohol polyoxyethylene ether sulfuric acid is 2-5: 1-3.
The temperature of the ice bath state described in the above preparation method is 0 to 4 ℃.
The dropping speed of the ammonium persulfate aqueous solution in the preparation method is 20-30 drops/min.
As a preferred technical solution, the aniline: lauryl alcohol polyoxyethylene ether sulfuric acid: cetostearyl alcohol: hydrochloric acid: the molar ratio of ammonium persulfate is 5:2.8:4:1: 5.
On the other hand, the invention also provides a high-flux detection method of the nitro polycyclic aromatic hydrocarbon in the rice crops, which comprises the following steps:
s1 preparation of nitro polycyclic aromatic hydrocarbon standard solution
S2 preparation of sample solution to be tested
S2-1, extracting: crushing and grinding a rice sample, sieving the rice sample by a 100-mesh metal sieve, weighing 2.0-5.0g of ground rice homogeneous sample in a 50mL sample tube, adding 5.0-10.0mL of pure water, uniformly mixing the ground rice homogeneous sample for 1-2min by using a vortex mixer, fully soaking the ground rice homogeneous sample for 10-20min, adding 10.0-20.0mL of acetonitrile, oscillating and extracting for 20-30min, ultrasonically extracting for 20-30min to obtain an extracting solution, then adding 1.0-2.0g of sodium chloride and 2.0-5.0g of anhydrous magnesium sulfate into the extracting solution at one time, oscillating for 1-2min, centrifuging for 5-10min at the speed of 4000 + 5000r/min, and taking the rice sample supernatant for later use;
s2-1 purification: transferring 1.0-2.0mL of rice sample supernatant into a micro centrifuge tube, adding 0.10-0.20g of anhydrous magnesium sulfate dehydrator and 0.02-0.04g of multi-wall carbon nano tube/polyaniline adsorbent, violently swirling for 1-2min, fully dispersing, decoloring and purifying, centrifuging for 5-10min at 4000 + 5000r/min, absorbing the supernatant and passing through a 0.22 mu m microporous filter membrane to obtain a rice sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
The mass ratio of the sodium chloride to the anhydrous magnesium sulfate in the step of extracting the rice sample described in the step S2-1 is 1: 1-5;
the mass ratio of the anhydrous magnesium sulfate to the multi-walled carbon nanotube/polyaniline in the rice sample purification step described in the step S2-2 is 2.5-10: 1.
In another aspect, the invention provides a high-flux detection method of nitro polycyclic aromatic hydrocarbon in soil, which comprises the following steps:
s1 preparation of nitro polycyclic aromatic hydrocarbon standard solution
S2 preparation of sample solution to be tested
S2-1, extracting: crushing a soil sample, sieving the crushed soil sample by a 100-mesh metal sieve, weighing 2.0-5.0g of ground rice homogeneous sample in a 50mL sample tube, adding 10.0-20.0mL of acetone/n-hexane, carrying out oscillation extraction for 20-30min, carrying out ultrasonic extraction for 20-30min, adding 0.5-1.0g of sodium chloride for salting out and 1.0-2.0g of anhydrous magnesium sulfate for dewatering, oscillating for 1-2min, centrifuging for 5-10min at 3000-4000r/min, and taking the supernatant of the soil sample for later use;
s2-1 purification: transferring 1.0-2.0mL of soil sample supernatant into a micro centrifuge tube, adding 0.05-0.10g of anhydrous magnesium sulfate dehydrator and 0.01-0.03g of multi-walled carbon nanotube/polyaniline adsorbent, violently swirling for 1-2min, fully dispersing, decoloring and purifying, centrifuging for 5-10min at 3000-4000r/min, absorbing the supernatant and passing through a 0.22-micrometer microporous filter membrane to obtain a soil sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
In the soil sample extraction step of the step S2-1, the mass ratio of the sodium chloride to the anhydrous magnesium sulfate for water removal is 1:1-4, and the volume ratio of acetone to n-hexane in acetone/n-hexane is 1: 1.
The mass ratio of the anhydrous magnesium sulfate to the multi-walled carbon nano tubes/polyaniline in the soil sample purification step in the step S2-2 is 5-10: 1-3.
The preparation of the nitro polycyclic aromatic hydrocarbon standard solution in the step S1 includes the following steps:
s1-1, preparing a standard intermediate solution of the nitro polycyclic aromatic hydrocarbon: respectively transferring 20 mu L of single standard solution of the nitro polycyclic aromatic hydrocarbon, and fixing the volume to 1mL by using acetonitrile to prepare 2.0 mu g/mL of standard intermediate solution;
s1-2, preparing a standard working solution of the nitro polycyclic aromatic hydrocarbon: diluting the standard intermediate solution of the nitro polycyclic aromatic hydrocarbon obtained in the step S1-1 by several times step by step to obtain a series of standard working solutions with the concentrations of 0.1, 0.5, 1.0, 5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively.
The single standard solution of carbamate and its thio-compounds described in step S1-1 above was purchased from Shanghai' S spectral reagent, Inc. (100. mu.g/mL).
The standard working solution needs to be prepared and used.
The detection method also comprises the detection of a blank sample, namely, a test in which a sample to be detected is not added, and the rest steps are completely the same as the analysis steps in the case of containing the sample.
Preferably, the apparatus used in step S3 is: an Agilent 1260 high performance liquid chromatograph is connected with a 6460 triple quadrupole mass spectrometer in series;
the chromatographic conditions are as follows:
liquid chromatography conditions:
a chromatographic column: ZoRBAX SB-C18(2.1*100mm*3.5μm)；
Flow rate: 0.4 mL/min;
column temperature: 40 ℃;
sample introduction amount: 10 mu L of the solution;
mobile phase: a is pure water, B is acetonitrile;
gradient elution procedure: 0-1min, 30% B; 1-5min, 30% -60% B; 5-20min, 60% -100% B; 20-25min, 100% B; 25-26min, 100% -30% B; 26-35min, 30% B;
mass spectrum conditions:
the scanning mode is as follows: negative ion scanning (APCI-);
spraying voltage: 4500V;
atomizing air pressure GS 1: 45 psi;
an ion source: atmospheric pressure ionization source APCI;
mass spectrum scanning mode: selecting an ion scanning SIM;
heating gas temperature: 300 ℃;
ion source temperature: 100 ℃;
removing the solvent gas: 10L/H;
residence time: 50 ms.
The invention has the beneficial effects that:
(1) the invention provides a novel fast-dispersing solid-phase extraction material multi-walled carbon nanotube/polyaniline polymer with strong applicability and a preparation method of the multi-walled carbon nanotube/polyaniline polymer, wherein the polymer has the characteristics of controllable particle size, high reuse rate and strong adsorption performance, can carry out double fast extraction analysis on rice and soil, realizes a key simple, fast and efficient sample analysis technology, and further realizes a high-flux detection method for nitro polycyclic aromatic hydrocarbon in rice crops and soil media thereof;
(2) the multi-walled carbon nanotube/polyaniline polymer adsorbent is used for purifying samples such as paddy, soil and the like, so that the interference of complex matrixes in the paddy, the soil and the like can be effectively reduced, and the detection accuracy is improved;
(3) the invention takes APCI-as an ion source, and successfully establishes a high-efficiency, accurate and simple analysis method for 10 kinds of nitro polycyclic aromatic hydrocarbons in two kinds of samples of rice and soil by optimizing mass spectrum and chromatographic conditions in an SIM mode, and the detection limit, the recovery rate and the precision of the method are satisfactory. Compared with the reported method, the method adopts a novel sample pretreatment material, has the advantages of better separation capability, higher analysis speed, higher sensitivity and the like, and is suitable for separation and analysis of trace amount of nitro polycyclic aromatic hydrocarbon in food and environmental samples.
Drawings
FIG. 1 is a high resolution scanning electron microscope image of a multi-walled carbon nanotube prepared according to a basic embodiment of the present invention;
FIG. 2 is a high resolution scanning electron microscope image of a multi-walled carbon nanotube/polyaniline prepared according to a basic embodiment of the present invention;
FIG. 3 is a total ion current chromatogram of a mixed standard solution with a concentration of 400. mu.g/L of 10 kinds of nitro polycyclic aromatic hydrocarbons;
wherein, the peak numbers 1-10 are respectively: 1: 1-nitronaphthalene; 2: 5-nitroacenaphthylene; 3: 2-nitrofluorene; 4: 3-nitrophenanthrene; 5: 9-nitroanthracene; 6: 1, 8-dinitropyrene; 7: 1-nitropyrene; 8: 3-nitrofluoranthene; 9: 6-nitrochrysin; 10: 6-Nitrobenzene [ a ] pyrene.
FIG. 4 is a quantitative ion flow chromatogram of a single component standard solution of 400. mu.g/L nitro polycyclic aromatic hydrocarbon;
wherein the content of the first and second substances,
FIG. 4-1 is a quantitative ion flow chromatogram of 400. mu.g/L1-nitronaphthalene standard solution;
FIG. 4-2 is a quantitative ion current chromatogram of 400. mu.g/L1-nitropyrene standard solution;
FIG. 4-3 is a quantitative ion current chromatogram of a standard solution of 400. mu.g/L1, 8-dinitropyrene;
FIGS. 4-4 are quantitative ion current chromatograms of 400. mu.g/L2-nitrofluorene standard solution;
FIGS. 4 to 5 are quantitative ion current chromatograms of 400. mu.g/L3-nitrofluoranthene standard solution;
FIGS. 4-6 are quantitative ion current chromatograms of 400. mu.g/L3-nitrophenanthrene standard solution;
FIGS. 4-7 are quantitative ion current chromatograms of 400. mu.g/L5-nitroacenaphthylene standard solution;
FIGS. 4-8 are quantitative ion flow chromatograms of 400. mu.g/L9-nitroanthracene standard solution;
FIGS. 4 to 9 are quantitative ion current chromatograms of 400. mu.g/L6-nitrochrysene standard solution;
FIGS. 4 to 10 are quantitative ion current chromatograms of a 400. mu.g/L6-nitrophenyl [ a ] pyrene standard solution;
FIG. 5 is a total ion chromatogram of a rice sample under different pretreatment conditions;
wherein, fig. 5a is comparative example 1, 5b is comparative example 2, 5c is comparative example 3, 5d is comparative example 4, and 5e is example 1.
FIG. 6 is a superimposed graph of total ion flow chromatograms of rice samples under different pretreatment conditions;
FIG. 7 is a total ion current chromatogram of a soil sample under different pretreatment conditions;
where, fig. 7a is comparative example 1, 7b is comparative example 2, 7c is comparative example 3, 7d is comparative example 4, and 7e is example 1.
FIG. 8 is a superimposed graph of total ion current chromatograms of soil samples under different pretreatment conditions.
Detailed Description
The features mentioned above in the description, or the features mentioned in the embodiments, may be combined arbitrarily. All the features disclosed in this specification may be combined in any suitable manner and each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The following examples are conducted under conditions specified, usually according to conventional conditions or according to conditions recommended by the manufacturer. All percentages and fractions are by weight unless otherwise specified.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are exemplary only.
Reagents and drugs used in the following examples:
the reagents and drug types required for the synthesis of the materials and the manufacturers of the drugs are shown in Table 3 below:
TABLE 3
| Reagent/medicine | Manufacturer/model |
| Multiwalled carbon nanotube | Commercially available, 15-25nm |
| Aniline | Analytically pure (vacuum distillation is required before use) |
| Ammonium persulfate | Chemical purity |
| Ethoxylated alkyl sulfuric acid | Industrial grade |
| Dodecyl alcohol polyoxyethylene ether sulfuric acid | Industrial grade |
| Hydrochloric acid | Chemical purity |
A single standard solution of the nitro polycyclic aromatic hydrocarbon used in the following examples was purchased from Shanghai's spectral reagent, Inc. (100. mu.g/mL) and stored at-20 ℃.
Preparation method of multi-walled carbon nanotube/polyaniline of basic embodiment
The method comprises the following steps: introducing nitrogen into a round-bottom three-mouth flask to remove oxygen, adding 2.0-5.0g of multi-walled carbon nano tube and 10.0-15.0mL of ethanol, ultrasonically homogenizing for 30 seconds for a short time, adding 50-100mL of deionized water and 0.025-0.10mol of first aniline, adding lauryl alcohol polyoxyethylene ether sulfuric acid and cetostearyl alcohol, quickly stirring at a constant temperature for 10-20min at a high speed, then adding 0.025-0.10mol of second aniline, finally adding 0.05-0.20mol of hydrochloric acid, controlling the reaction temperature in an ice bath state, continuously stirring for 30-50min, dropwise adding 0.05-0.20mol of ammonium persulfate aqueous solution, continuously stirring at a high speed for reacting for 6-10h, and obtaining a product after the reaction is finished; demulsifying the product with acetone, filtering the emulsion with a G3/G4 funnel, centrifuging, repeatedly washing with acetone-water to neutrality, and vacuum drying at 60-80 deg.C to obtain the multi-walled carbon nanotube/polyaniline polymer.
In the preparation method, the molar ratio of the first part of aniline to the lauryl alcohol polyoxyethylene ether sulfuric acid is 2-5: 1-3.
The temperature of the ice bath state described in the above preparation method is 0 to 4 ℃.
The dropping speed of the ammonium persulfate aqueous solution in the preparation method is 20-30 drops/min.
As a preferred technical solution, the aniline: lauryl alcohol polyoxyethylene ether sulfuric acid: cetostearyl alcohol: hydrochloric acid: the molar ratio of ammonium persulfate is 5:2.8:4:1:5
Embodiment 1 a high throughput detection method for nitro polycyclic aromatic hydrocarbons in rice crops, comprising the following steps:
s1 preparation of nitro polycyclic aromatic hydrocarbon standard solution
S1-1, preparing a standard intermediate solution of the nitro polycyclic aromatic hydrocarbon: respectively transferring 20 mu L of single standard solution of the nitro polycyclic aromatic hydrocarbon, and fixing the volume to 1mL by using acetonitrile to prepare 2.0 mu g/mL of standard intermediate solution;
s1-2, preparing a standard working solution of the nitro polycyclic aromatic hydrocarbon: diluting the standard intermediate solution of the nitro polycyclic aromatic hydrocarbon obtained in the step S1-1 by a plurality of times step by step to obtain a series of standard working solutions with the concentrations of 0.1, 0.5, 1.0, 5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively;
s2 preparation of sample solution to be tested
S2-1, extracting: crushing and grinding a rice sample, sieving the rice sample by using a 100-mesh metal sieve, weighing 2.0g of ground rice homogeneous sample in a 50mL sample tube, adding 5.0mL of pure water, uniformly mixing the pure water with a vortex mixer for 1min, fully soaking the mixture for 10min, adding 10.0mL of acetonitrile, oscillating and extracting the mixture for 20min, ultrasonically extracting the mixture for 20min to obtain an extracting solution, then adding 1.0g of sodium chloride and 2.0g of anhydrous magnesium sulfate into the extracting solution at one time, oscillating the extracting solution for 1min, centrifuging the extracting solution for 5min at 4000r/min, and taking the rice sample supernatant for later use;
s2-1 purification: transferring 1.0mL of rice sample supernatant into a micro centrifugal tube, adding 0.10 anhydrous magnesium sulfate dehydrator and 0.02g of multi-wall carbon nano tube/polyaniline adsorbent, violently swirling for 1min, fully dispersing, decolorizing and purifying, centrifuging for 5min at 4000r/min, absorbing the supernatant, and filtering through a 0.22 mu m microporous filter membrane to obtain a rice sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
Embodiment 2 a high-throughput detection method of nitro polycyclic aromatic hydrocarbon in soil, comprising the following steps:
s1 preparation of nitro polycyclic aromatic hydrocarbon standard solution
S1-1, preparing a standard intermediate solution of the nitro polycyclic aromatic hydrocarbon: respectively transferring 20 mu L of single standard solution of the nitro polycyclic aromatic hydrocarbon, and fixing the volume to 1mL by using acetonitrile to prepare 2.0 mu g/mL of standard intermediate solution;
s1-2, preparing a standard working solution of the nitro polycyclic aromatic hydrocarbon: diluting the standard intermediate solution of the nitro polycyclic aromatic hydrocarbon obtained in the step S1-1 by a plurality of times step by step to obtain a series of standard working solutions with the concentrations of 0.1, 0.5, 1.0, 5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively;
s2 preparation of sample solution to be tested
S2-1, extracting: crushing a soil sample, sieving the crushed soil sample by a 100-mesh metal sieve, weighing 5.0g of ground rice homogeneous sample in a 50mL sample tube, adding 20.0mL acetone/n-hexane, oscillating and extracting for 30min, ultrasonically extracting for 30min, adding 1.0g of sodium chloride for salting out and 2.0g of anhydrous magnesium sulfate for dewatering, oscillating for 2min, centrifuging for 5-10min at 4000r/min, and taking a soil sample supernatant for later use;
s2-1 purification: transferring 2.0mL of soil sample supernatant into a micro centrifuge tube, adding 0.10g of anhydrous magnesium sulfate dehydrator and 0.03g of multi-walled carbon nanotube/polyaniline adsorbent, violently swirling for 2min, fully dispersing, decolorizing and purifying, centrifuging for 10min at 4000r/min, absorbing the supernatant and passing through a 0.22 mu m microporous filter membrane to obtain a soil sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
The detection conditions for examples 1-2 were:
the instrument comprises the following steps: an Agilent 1260 high performance liquid chromatograph is connected with a 6460 triple quadrupole mass spectrometer in series;
conditions of liquid chromatography
A chromatographic column: ZoRBAX SB-C18(2.1*100mm*3.5μm)；
Flow rate: 0.4 mL/min;
column temperature: 40 ℃;
sample introduction amount: 10 mu L of the solution;
mobile phase: a is pure water, B is acetonitrile;
gradient elution procedure: 0-1min, 30% B; 1-5min, 30% -60% B; 5-20min, 60% -100% B; 20-25min, 100% B; 25-26min, 100% -30% B; 26-35min, 30% B;
mass spectrum conditions:
the scanning mode is as follows: negative ion scanning (APCI-);
spraying voltage: 4500V;
atomizing air pressure GS 1: 45 psi;
an ion source: atmospheric pressure ionization source APCI;
mass spectrum scanning mode: selecting an ion scanning SIM;
heating gas temperature: 300 ℃;
ion source temperature: 100 ℃;
removing the solvent gas: 10L/H;
residence time: 50 ms.
Table 1 shows the retention times and the quantitative ion of 10 kinds of nitro polycyclic aromatic hydrocarbons
Comparative example 1:
the sample introduction method was performed without the addition of the multi-walled carbon nanotube/polyaniline adsorbent, otherwise the same as example 1.
Comparative example 2:
pretreatment of PSA dispersion solid phase extraction, replacing the multi-walled carbon nanotube/polyaniline adsorbent with 0.02g PSA, and the rest is the same as example 1.
Comparative example 3:
C18pretreatment by a dispersion solid phase extraction method, namely replacing a multi-wall carbon nano tube/polyaniline adsorbent with 0.02g C18Otherwise, the same procedure as in example 1 was repeated.
Comparative example 4:
PSA+C18pretreatment by a dispersion solid phase extraction method, namely replacing a multi-wall carbon nano tube/polyaniline adsorbent by 0.02g of PSA + C18(mass ratio 1:1), the same as in example 1.
Effect verification
1. And (3) measuring the content of the nitro polycyclic aromatic hydrocarbon in the sample:
the sample solutions to be tested, i.e., the rice and soil sample solutions, were prepared by the methods of examples 1-2 and comparative examples 1-4, respectively, and labeled as sample 1 (sample 1-1, sample 1-2, sample 1-3, sample 1-4, sample 1-5, and sample 1-6, respectively, according to different groups) and sample 2 (sample 2-1, sample 2-2, sample 2-3, sample 2-4, sample 2-5, and sample 2-6, respectively, according to different groups), and the concentrations of 10 kinds of nitro polycyclic aromatic hydrocarbons in sample 1 and sample 2 were analyzed.
The specific calculation formula is as follows:
wherein the content of the first and second substances,
x is the content of the nitro polycyclic aromatic hydrocarbon in the sample, and the unit is microgram per kilogram (mu g/kg), C is the concentration of a certain component in the liquid to be tested obtained by substituting the component into a standard curve, and the unit is nanogram per milliliter (ng/mL), V is the final constant volume of the liquid to be tested of the sample, and the unit is milliliter (mL), 1000 is the unit conversion multiple, m is the sample weighing mass, and the unit is gram (g), and f is the dilution multiple.
The detection shows that: the concentration of 10 kinds of nitro polycyclic aromatic hydrocarbons in the paddy and the soil are analyzed simultaneously by the method, and the result shows that the concentration of 10 kinds of nitro polycyclic aromatic hydrocarbons in the two samples is lower than the detection limit.
As can also be seen in connection with fig. 5-8:
it can be seen from FIGS. 5 and 7 that no component was detected in both sample 1 and sample 2 of this test example 1 and comparative examples 1 to 4 (the total ion current chromatogram can determine whether a target component was detected in the sample by the characteristic peak at a specific time in combination with the identification of the target component qualitative and quantitative ion pairs).
The superposed graph of the total ion chromatogram is the superposed graph of the total ion chromatogram under five different pretreatment conditions, and is attached with the test graphs of two samples of soil and rice for reference.
2. Determination of standard curve, linear range, detection limit and quantification limit
Analysis and detection of matrix correction curves, correlation coefficients, detection limits and quantification limits are carried out on 10 kinds of nitro polycyclic aromatic hydrocarbons, and test results are shown in table 2 below.
Table 2 shows the standard curve, linear range, detection limit and quantitative limit of 10 kinds of nitro polycyclic aromatic hydrocarbons
From the test results of table 2 above, it can be seen that: the linearity is good in the curve range of 0.1 mu g/L-200 mu g/L, the detection Limit (LOD) of 10 components is 0.10 mu g/kg-5.56 mu g/kg, the quantification Limit (LOQ) is 0.33 mu g/kg-18.53 mu g/kg, and the correlation coefficient (R)2) Is 0.9997-0.9999.
3. Detection of standard recovery rate and precision
The mixed standard solution of the nitro polycyclic aromatic hydrocarbon is added into a representative sample, the addition amounts of the low, the middle and the high are respectively 10, 100 and 200 mu g/kg, each sample is subjected to parallel measurement and is continuously measured for 6 times, the average recovery rate of the 10 nitro polycyclic aromatic hydrocarbons is calculated to be 88.4 to 97.3 percent, and the relative standard deviation RSD (%) is 1.9 to 5.2 percent.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art having reference to the foregoing specification and claims; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (19)
1. A high-throughput method for detecting the content of nitro polycyclic aromatic hydrocarbon is characterized in that: the method comprises the following steps:
s1, preparing a nitro polycyclic aromatic hydrocarbon standard solution;
s2, preparing a sample solution to be detected;
s2-1 extraction: crushing and grinding a sample, sieving, weighing the sample in a sample tube, adding a solution for soaking, performing ultrasonic extraction to obtain an extracting solution, then adding sodium chloride and anhydrous magnesium sulfate into the extracting solution at one time, oscillating, centrifuging for 5-10min at 4000-;
s2-2 purification: transferring the sample supernatant into a micro-centrifuge tube, adding an anhydrous magnesium sulfate water removing agent and a multi-walled carbon nanotube/polyaniline adsorbent, violently swirling, fully dispersing, decolorizing and purifying, centrifuging at 4000-;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
Performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to a standard curve by an external standard method;
the sample is one of rice crops or soil.
2. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 1, wherein: the high-flux detection method for the nitro polycyclic aromatic hydrocarbon in the rice crops comprises the following steps:
s1 preparation of nitro polycyclic aromatic hydrocarbon standard solution
S2 preparation of sample solution to be tested
S2-1 extraction: crushing and grinding a rice sample, sieving the rice sample by a 100-mesh metal sieve, weighing 2.0-5.0g of ground rice homogeneous sample in a 50mL sample tube, adding 5.0-10.0mL of pure water, uniformly mixing the ground rice homogeneous sample for 1-2min by using a vortex mixer, fully soaking the ground rice homogeneous sample for 10-20min, adding 10.0-20.0mL of acetonitrile, oscillating and extracting for 20-30min, ultrasonically extracting for 20-30min to obtain an extracting solution, then adding 1.0-2.0g of sodium chloride and 2.0-5.0g of anhydrous magnesium sulfate into the extracting solution at one time, oscillating for 1-2min, centrifuging for 5-10min at the speed of 4000 + 5000r/min, and taking the rice sample supernatant for later use;
s2-2 purification: transferring 1.0-2.0mL of rice sample supernatant into a micro centrifuge tube, adding 0.10-0.20g of anhydrous magnesium sulfate dehydrator and 0.02-0.04g of multi-wall carbon nano tube/polyaniline adsorbent, violently swirling for 1-2min, fully dispersing, decoloring and purifying, centrifuging for 5-10min at 4000 + 5000r/min, absorbing the supernatant and passing through a 0.22 mu m microporous filter membrane to obtain a rice sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
3. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 2, wherein: in the step of extracting the rice sample described in the step S2-1, the mass ratio of the sodium chloride to the anhydrous magnesium sulfate is 1: 1-5.
4. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 2, wherein: the mass ratio of the anhydrous magnesium sulfate to the multi-walled carbon nano tubes/polyaniline in the rice sample purification step in the step S2-2 is 2.5-10: 1.
5. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 1, wherein: the high-flux detection method of the nitro polycyclic aromatic hydrocarbon in the soil comprises the following steps:
s1, preparing a nitro polycyclic aromatic hydrocarbon standard solution;
s2, preparing a sample solution to be detected;
s2-1 extraction: crushing a soil sample, sieving the crushed soil sample by a 100-mesh metal sieve, weighing 2.0-5.0g of ground rice homogeneous sample in a 50mL sample tube, adding 10.0-20.0mL of acetone/n-hexane, carrying out oscillation extraction for 20-30min, carrying out ultrasonic extraction for 20-30min, adding 0.5-1.0g of sodium chloride for salting out and 1.0-2.0g of anhydrous magnesium sulfate for dewatering, oscillating for 1-2min, centrifuging for 5-10min at 3000-4000r/min, and taking the supernatant of the soil sample for later use;
s2-2 purification: transferring 1.0-2.0mL of soil sample supernatant into a micro centrifuge tube, adding 0.05-0.10g of anhydrous magnesium sulfate dehydrator and 0.01-0.03g of multi-walled carbon nanotube/polyaniline adsorbent, violently swirling for 1-2min, fully dispersing, decoloring and purifying, centrifuging for 5-10min at 3000-4000r/min, absorbing the supernatant and passing through a 0.22-micrometer microporous filter membrane to obtain a soil sample solution to be detected;
s3, drawing a standard curve
Injecting the standard solution series into a liquid chromatogram-tandem mass spectrometer, and drawing a standard working curve by taking the quantitative ion peak area of the nitro polycyclic aromatic hydrocarbon as a vertical coordinate and the concentration of the corresponding nitro polycyclic aromatic hydrocarbon as a horizontal coordinate;
s4, analysis and detection
And (4) performing on-machine determination on the sample solution to be detected prepared in the step S2 and the standard solution prepared in the step S1, and calculating the concentration of the nitro polycyclic aromatic hydrocarbon in the sample solution to be detected according to the standard curve by an external standard method.
6. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 5, wherein: in the soil sample extraction step of the step S2-1, the mass ratio of sodium chloride to anhydrous magnesium sulfate for water removal is 1: 1-4.
7. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 5, wherein: in the acetone/n-hexane, the volume ratio of acetone to n-hexane in the step S2-1 is 1: 1.
8. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 5, wherein: in the step of purifying the soil sample in the step S2-2, the mass ratio of the anhydrous magnesium sulfate to the multi-walled carbon nano tubes/polyaniline is 5-10: 1-3.
9. A high-throughput method for detecting the content of nitro polycyclic aromatic hydrocarbons according to any one of claims 1, 2 and 5, wherein: the preparation of the nitro polycyclic aromatic hydrocarbon standard solution in the step S1 comprises the following steps:
s1-1, preparing a standard intermediate solution of the nitro polycyclic aromatic hydrocarbon: respectively transferring 20 mu L of single standard solution of the nitro polycyclic aromatic hydrocarbon, and fixing the volume to 1mL by using acetonitrile to prepare 2.0 mu g/mL of standard intermediate solution;
s1-2, preparing a standard working solution of the nitro polycyclic aromatic hydrocarbon: diluting the standard intermediate solution of the nitro polycyclic aromatic hydrocarbon obtained in the step S1-1 by several times step by step to obtain a series of standard working solutions with the concentrations of 0.1, 0.5, 1.0, 5.0, 10.0, 100.0, 200.0, 500.0 and 1000.0ng/mL respectively.
10. A high-throughput method for detecting the content of nitro polycyclic aromatic hydrocarbons according to any one of claims 1, 2 and 5, wherein: the instrument used in step S3 is: an Agilent 1260 high performance liquid chromatograph is connected with a 6460 triple quadrupole mass spectrometer in series;
the chromatographic conditions are as follows: a chromatographic column: ZoRBAX SB-C18(2.1*100mm*3.5μm)；
Liquid chromatography conditions:
flow rate: 0.4 mL/min;
column temperature: 40 ℃;
sample introduction amount: 10 mu L of the solution;
mobile phase: a is pure water, B is acetonitrile;
gradient elution procedure: 0-1min, 30% B; 1-5min, 30% -60% B; 5-20min, 60% -100% B; 20-25min, 100% B; 25-26min, 100% -30% B; 26-35min, 30% B;
mass spectrum conditions:
the scanning mode is as follows: negative ion scanning (APCI-);
spraying voltage: 4500V;
atomizing air pressure GS 1: 45 psi;
an ion source: atmospheric pressure ionization source APCI;
mass spectrum scanning mode: selecting an ion scanning SIM;
heating gas temperature: 300 ℃;
ion source temperature: 100 ℃;
removing the solvent gas: 10L/H;
residence time: 50 ms.
11. A high-throughput method for detecting the content of nitro polycyclic aromatic hydrocarbons according to any one of claims 1, 2 and 5, wherein: the multi-walled carbon nanotube/polyaniline adsorbent described in step S2-2 was prepared by the following method: putting the multi-walled carbon nano-tube into a three-neck flask, adding an emulsifier, a co-emulsifier, a dopant and an initiator into the three-neck flask, and preparing the multi-walled carbon nano-tube/polyaniline polymer by adopting an emulsion polymerization method.
12. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 11, wherein: the emulsifier is dodecyl alcohol polyoxyethylene ether sulfuric acid; the auxiliary emulsifier is cetearyl alcohol; the dopant is hydrochloric acid; the initiator is ammonium persulfate.
13. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 11, wherein: the reaction temperature of the emulsion polymerization method is 0-4 ℃, and the reaction time is 5-6 h.
14. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 11, wherein: the molar ratio of the emulsifier to the co-emulsifier to the dopant to the initiator is 2.8:4:1: 5.
15. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to any one of claims 12 to 14, wherein: the preparation method of the multi-wall carbon nanotube/polyaniline adsorbent comprises the following steps: introducing nitrogen into a round-bottom three-mouth flask to remove oxygen, adding 2.0-5.0g of multi-walled carbon nano tube and 10.0-15.0mL of ethanol, ultrasonically homogenizing for 30 seconds for a short time, adding 50-100mL of deionized water and 0.025-0.10mol of first aniline, adding lauryl alcohol polyoxyethylene ether sulfuric acid and cetostearyl alcohol, quickly stirring at a constant temperature for 10-20min at a high speed, then adding 0.025-0.10mol of second aniline, finally adding 0.05-0.20mol of hydrochloric acid, controlling the reaction temperature in an ice bath state, continuously stirring for 30-50min, dropwise adding 0.05-0.20mol of ammonium persulfate aqueous solution, continuously stirring at a high speed for reacting for 6-10h, and obtaining a product after the reaction is finished; demulsifying the product with acetone, filtering the emulsion with a G3/G4 funnel, centrifuging, repeatedly washing with acetone-water to neutrality, and vacuum drying at 60-80 deg.C to obtain the multi-walled carbon nanotube/polyaniline polymer.
16. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 15, wherein: the molar ratio of the first part of aniline to the lauryl alcohol polyoxyethylene ether sulfuric acid is 2-5: 1-3.
17. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 15, wherein: the temperature of the ice bath state is 0-4 ℃.
18. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 15, wherein: the dropping speed of the ammonium persulfate aqueous solution is 20-30 drops/min.
19. A high-throughput method for detecting nitro polycyclic aromatic hydrocarbon content according to claim 15, wherein: the aniline: lauryl alcohol polyoxyethylene ether sulfuric acid: cetostearyl alcohol: hydrochloric acid: the molar ratio of ammonium persulfate is 5:2.8:4:1: 5.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080190855A1 (en) * | 2005-05-06 | 2008-08-14 | Isis Innovation Limited | Derivatised Carbon |
| US20140103558A1 (en) * | 2012-08-27 | 2014-04-17 | U.S.A., as represented by the Administrator of the National Aeronautics and Space Administration | Polyaniline/carbon nanotube sheet nanocomposites |
| CN106883606A (en) * | 2017-03-03 | 2017-06-23 | 深圳市佩成科技有限责任公司 | The preparation method of PANI/MWCNTs composites |
| CN110681184A (en) * | 2019-09-29 | 2020-01-14 | 华中师范大学 | Multi-walled carbon nanotube/polyaniline composite coating based in-pipe solid phase micro-extraction column and online micro-extraction method |
| CN111007192A (en) * | 2019-12-23 | 2020-04-14 | 中国农业科学院农产品加工研究所 | Method for detecting nitro polycyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon in soil |
| RU2719578C1 (en) * | 2019-05-20 | 2020-04-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method of determining polycyclic aromatic hydrocarbons in soils and bottom sediments |
| CN111650317A (en) * | 2020-07-15 | 2020-09-11 | 南通市疾病预防控制中心 | High-flux detection method for polycyclic aromatic hydrocarbons in traditional Chinese medicinal materials |
-
2021
- 2021-12-17 CN CN202111552830.1A patent/CN114324681A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080190855A1 (en) * | 2005-05-06 | 2008-08-14 | Isis Innovation Limited | Derivatised Carbon |
| US20140103558A1 (en) * | 2012-08-27 | 2014-04-17 | U.S.A., as represented by the Administrator of the National Aeronautics and Space Administration | Polyaniline/carbon nanotube sheet nanocomposites |
| CN106883606A (en) * | 2017-03-03 | 2017-06-23 | 深圳市佩成科技有限责任公司 | The preparation method of PANI/MWCNTs composites |
| RU2719578C1 (en) * | 2019-05-20 | 2020-04-21 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") | Method of determining polycyclic aromatic hydrocarbons in soils and bottom sediments |
| CN110681184A (en) * | 2019-09-29 | 2020-01-14 | 华中师范大学 | Multi-walled carbon nanotube/polyaniline composite coating based in-pipe solid phase micro-extraction column and online micro-extraction method |
| CN111007192A (en) * | 2019-12-23 | 2020-04-14 | 中国农业科学院农产品加工研究所 | Method for detecting nitro polycyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon in soil |
| CN111650317A (en) * | 2020-07-15 | 2020-09-11 | 南通市疾病预防控制中心 | High-flux detection method for polycyclic aromatic hydrocarbons in traditional Chinese medicinal materials |
Non-Patent Citations (2)
| Title |
|---|
| SHARMA, A.K ETC: "Synthesis and study of polyaniline/MWCNT composite for optoelectronic application" * |
| 张琼瑶等: "新型涂层搅拌棒的研究进展" * |
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